Coated articles and textiles and emulsions for producing them



Patented Dec. 29, 1953 COATED ARTICLES AND TEXTILES AND EMULSIONS FOR PRODUCING THEM Carl Schlatter, Wilmington, Del., and John-l3. Eisen, Springfield, and George D. Jefierson,

Kennett Square,

No Drai'ving. ApplicationMarch 19, 1949, Serial No. 82,482

This invention relates to compositions iory dressing and finishing textile yarns, cords, fab. rics and other articles, such as paper, felts, and films, such as sheets of-cellophane. it isparticularly concerned with compositions which are adapted to prepare the articles to which they are applied for further treatment with coatings of various kinds, such as, in the case of the prepa ration of tire cords, with a rubber latex composition. However, the compositions are also adaptable for the dressing of articles for temporary purposes such as for the lubricating or siz ing of yarns in weaving and knitting processes,

of the invention is to provide a conditioning compositionfor textiles and other articles which 18 claims. 01. 57-153) pcnents are balanced to provide an ester of :solid waxy character rather than of a. liquid consistency. Examples of the waxy ester lubricant are as (follows: sorbitan or mannitan monopalmitate, sorbitan or mannitan dipalmitate, sorbitan or niannitan monoor distearatc, sorbitan or mannitan palmitate laurate, mixtures of any of these esters, as well as mixtures of one or more thereof with sorbitan or mannitan monoor dilaurate, which have a waxy consistency. Other lubricants may be added, suchas any mineral oil whether of naphthenic, aliphatic, aromatic, or mixed character, fats or oils of vegetable, animal or fish origin which may also be hydrogenated, if

- desired.

As the water-scluble or dispersible binding colloid, there may be used polyvinyl alcohol, the alkali metal or NI-Ir salts of copolymers of styrene and iumaric (maleic) acids (such as the product them water-dispersible or preferably water-soluis not water-repellent so that the dressed articles readily accept further coatings from aqueous media, such as rubber latex in the production of cords which can be 'used in the production of rubber articles such as tires, belts, hose, and the:

an emulsion or dispersion and comprises a lubricant comprising a waxy partial ester of an anhydropolyhydric alcohol with a higher iatty acid as the dispersed phase, a water-soluble or dispersible binding colloid, a poly-oxy ethylene ether of castor oil or hydrogenated castor oil having about 80 to200 ethoxy groups-in the molecule as an emulsifier or emulsion stabilizer, and analk'aline buffer. 7 g

The lubricant comprises as an essential constituent a waxy partial ester, a waxy partial.

mixed ester, or a waxy mixture of partial esters,

of'an anhydro hexanydric alcohol and a fatty acid of at least 16 carbon atoms. When a mixed ester or mixture of esters is" used, a part of the fatty acid component may be derivedfrom acids having at least 12 carbon atoms. The acid com= ble, also the salts of such copolymers and polymers, sodium carboxymethylcellulose of low, me-

dium or high viscosity, water-soluble methyl cellulose, water-soluble hydroxyethyl cellulose, water-soluble polymers of dime'thylhydantoin formaldehyde, gelatine, chromated gelatines, starch, and starch degradation products such as dextrines or mixtures of two or more of these colloids.

'7 As the alkaline bufier, the alkalimetal salts of the higher fatty acids having at least 12 carbon atoms are extremely valuable, such as sodium The proportion of water may vary depending on the intended use. When the composition is intended for the treatment of rayon for making tire cords, enough water is added to make a total of 1000 parts by weight.

The relative proportions between the several ingredients are designed to enable the several ingredients to impart to the final product the several functions for which they are intended. The ester constituent of the lubricant is scourable and hydrophillic and a minimum of 0.5 parts by weight is necessary regardless of whether or not another lubricant is present. Apparently the lubricant plasticizes the binder which enables the small amount of binder to hold the filaments together even through flexing that occurs during such operations as winding while permitting smooth slipping between filaments during twisting. The main purpose of lubricant is to protect the yarns or other structures and lubricate them as they pass over guides in the subsequent processing.

Enough binder is provided to hold the untwisted filaments together in a yarn during passage through the textile machines but an excessive amount is avoided to prevent any deposit on the drier drums and shedding on the guides. The proportion of binder is used in an amount which is sufficient enough to hold untwisted filaments together but insufficient to interfere with uniform twisting of the yarn containing the composition. The preferred proportions of binder are between 1 part in 2 parts of total solids and 1 part in 4 parts of total solids and the optimum is 1 part of binder in 3 parts of total solids when the composition is intended for such uses as application to rayon for making tire cords. For purposes such as setting the twist in lively twisted yarns, slashing (i. e. warp sizing), the binder is preferably increased so that there is 1 part of binder in 2 parts of total solids up to 3 parts of binder in 4 parts of total solids.

When no liquid lubricant is present; that is, when the lubricant consists entirely of the waxy ester, the amount of emulsifier must be at least one half the amount of lubricant by weight. When a liquid lubricant is present it is necessary to use at least as much of the emulsifier as the lubricant by weight and it is preferred to use 4 to 7 times as much emulsifier as liquid lubricant.

The composition is applied to the articles for various purposes. the table above is entirely suitable when applying the material to wet filaments or yarns in amounts satisfactory for the production of tire cord, in which application, the amount of dressing upon the dried article is generally from about ii; to and preferably between 1 and 2% by weight of the yarn. The same concentration may be used for applying a knitting finish for lubricating purposes to dry yarns. For some other purposes, the concentration is preferably increased. For example, the concentration may be as much as doubled when it is desired to use the composition for warp-sizing of yarns. The concentration may be doubled or even almost tripled in applying it to yarns or cordshaving a lively twist, such as tire cords or crepe-twisted yarns having 25 to 75 turns per inch twist, for the purpose of setting the twist therein. The amount of dressing upon the yarn in the case of warp-sizing may vary from 5 to by weight of the yarn, whereas in twist-setting 5 to of the composition by weight of the yarn may be present.

The composition, as stated, may be applied to various articles. For example, it may be applied to untwisted bundles of filaments which may be in the wet or dry condition. For example, it may be applied to the freshly spun re- The concentration given in v generated cellulose rayon filament bundles hav= ing from 40 to 1200 or more denier size. The larger denier yarns, say from 500 to 2,000 denier, may receive the composition of the present invention before their first drying and before their twisting. The composition is also advantageous for the application to freshly spun artificial filements which are collected without twist or with very low twist when first produced. By apply ing the composition to the freshly spun filaments before collection, the binder colloid in the composition imparts sufficient body to the dried product to hold the filaments together and thereby the application in this instance serves to facilitate subsequent unwinding of the collected package of yarn while preventing rupture of filaments therein which would otherwise be caused by an overlapping and interlocking or tangling of filaments which contact one another in adjacent convolutions of the package. By applying the composition to the relatively untwisted yarns before collection, the filaments in the individual yarns are bound together and prevented from catching on the filaments of adjacent yarns.

The composition may be applied to yarns comprising filaments of regenerated cellulose produced from viscose, cuprammonium, cellulose, nitrocellulose, and the like, or of cellulose esters, such as cellulose acetate, propiona-te or cellulose propionate butyrate; cellulose ethers, such as ethyl cellulose, benzyl cellulose, either of the solvent-soluble type or of the water-insoluble, alkali-soluble type, casein or other proteins, synthetic resins, such as nylon, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, polyethylene, and also copolymers of vinyl chloride, with vinyl acetate, acrylonitrile, vinylidene chloride, and the like. The composition may also be applied to yarns comprising fibers of natural origin, such as cotton, wool, silk and the like. The composition may be applied to any of the synthetic or natural fiber yarns, or cords or fabrics formed therefrom, for any of the purposes mentioned hereinabove, such as for a knitting lubricant, a tire cord preparatory finish, a Warp-size, or the like. The composition may be applied in any of the concentrations mentioned hereinabove to other articles such as papers, felts, cellophane or cellulose acetate sheets as a priming coating to facilitate the acceptance by the article of a subsequent coating of other material, such as a rubber latex.

In the specific application of the composition for the formation of tire cord, the composition may be applied to individual multi-filament bundles either in twisted or untwisted condition which are later plied together into a multi-ply cord structure. In the plying, the individual yarns may be given any twist as in a separate step preliminary to the final doubling into the form of cording. Also, the individual yarn after being twisted singly may be plied into strands,

several of which are later plied into a final cord.

In the following examples which are illustrative of the invention, the parts are given by weight.

Example I In 10 parts of water, 0.25 part of polyvinyl alcohol was dissolved and 0.2 part of sodium oleate was added. This mixture was heated for one hour at to C. Sorbitan monopalmitate (0.15 part) was fused with 0.4 part of castor oil modified with ethylene oxide and having an average of 127 ethoxy groups in the molecule. This aesanaa mijxtureof lubricant and emulsifier was added to the buffer-binder solution with agitation and an emulsion resulted which is hereinafter referred to as a stock emulsion for convenience. This stock emulsion was then diluted with 89 parts of water and was then applied to a wet, freshly spun and processed 1100 denier, 480 filament viscous rayon yarn while it was in untwisted condition on the last stage of treatmenton a thread-advancing thread storage reel just prior to the drying stage of a continuous rayon spinning and processing machine, as described, for example in application Serial No. 532,328, filed April 22, 1944, now Patent 2,516,157. The yarn then passed to a succeeding thread-advancing thread-storage device upon whichit was dried. Thereafter the arn was collected without twist. The resulting yarn was thereafter twisted to a total of 14 turns per inch of Z-twist and two strands of the resulting yarn were then plied together with about 11 turns per inch in the opposite direction. The resulting cord, containing about 1% by weight of the composition, had a high oven-dry tensile strength, excellent fatigue resistance, excellent latex pick-up, and good adhesion to rubber in the final product.

Example II The procedure of ExampleI was followed with the .same constituents, except the proportions were changed as follows:

The procedure of Example II was followed, the only change being that the modified castor oil had an average of 200ethoxy groups in the molecule.

Example IV Sodium carboxymethyl cellulose of medium, viscosity (0.25 part) was dissolved in parts of hot. water (50 to 60 C.) and 0.2 part of sodium oleate was added. A mixture of 0.15 part sorbitan monopalmitate and 0.4 part of modified castor oil having an average of 127 ethoxy groups per molecule, obtained by fusion as in Example I, was added to the buifer-binder solution with agitation to, produce a stable, substantially uniform stock emulsion. The stock'emulsion thus obtained was diluted with 89 parts of water and applied as in Example I to rayon yarns for the Example VI The procedure of Example IV was followed but the constituents and proportions were as follows:

Castor oil modified with 127 ethoxy groups 0.2 7

NOTE.A1ql1ad HT is a mixture of alkyl or alkenyl trimethyl ammonium chloride in which the alkyl groups have from 8 to l8'carbon atoms and are saturated or unsaturated; they are chiefly the 16 to 18 carbon chains obtained by the hydrogenation of tallow fatty acids.

Example VII The procedure of Example IV was followed except that the sodium oleate was replaced with a] corresponding amount of Arquad HT.

Example VIII The stock emulsion obtained in Example I was dilutedwith 70 parts of water and then'applied by means of rollers dipping into a container of the emulsion, to a warp of yarn and dried. The warp containing 10% of the composition by weight of the yarn was woven with complete satisfaction.

Example IX The stock emulsion made in. accordance with- Example IV but containing 0.7 part of sodium. carboxymethyl cellulose instead of 0.25 was di-' luted to a concentration of 25% and applied to crepe-twisted yarns including 15.0 denier, 75, fila ment rayon yarns having 60 turns. of twist per' inch, such, yarns having a lively twist prior to treatment, and after drying the composition on the yarns, they were found to contain approximately 14% by weight of the twist-setting medium based on the weight of the yarn. The

yarn could then be used in knitting full-fashioned hosiery and making woven crepe fabrics without any tendency to exhibit liveliness of twist during the operation.

Example X The stock emulsion obtained, in Example I, and; diluted with 60 parts of water was applied to a. multi-filament bundle of untwisted cellulose acea thread-advancing thread-storage device on which it was dried and after collection it was found to contain 3% of the dressing by weight of the yarn. The collected package of yarn was then passed through a rewinding operation in which no trouble was encountered in respect to the tendency, during unwinding, of the filaments to tangle in adjacent convolutions of the yarn on the original collection package.

Example XI I The stock emulsionobtainedas in Example IV was diluted with 50 parts of waterandwas applied to a sewing thread of. cotton. It was applied during the rewinding operation and was dried continuously as it proceeded from the point The of application to the rewind ing package. thread received a coating of 7% by weight of the yarn.

Example XII A cellophane sheet was passed through a bath containing the stock emulsion obtained in Example IV and diluted with 120 parts of water. Thereafter, the coated sheet was dried and passedthrough a latex bath to produce a rubber .coating thereon. The product was dried and vulcanized and was found to be waterproof. The product was useful for making rug antislip bases, other friction materials, wall coverings, childrens sohoolbooks, brief cases and the like.

Example XIII The procedure of Example XII was followed except that the stock emulsion included 0.2 part of a mineral oil and the cellophane base sheet was replaced with a woven and knitted rayon fabric. The resulting material was useful as a material for making raincoats, moistureproof aprons, bathing caps, and baby pants.

The present invention provides a composition which is a stable transparent emulsion or dispersion, easy to apply uniformly readily dilutable to provide any desired concentration derivable from a common stock emulsion. It is especially useful for application to textile yarns and cords, such as tire cords. In such application it is characterized by freedom from stripping or shedding on guides or drier drums. Yarns, cords and other structures carrying the composition readily accept further coating from aqueous media, such as the latex used for tire cords, because they have excellent wettability and are not water-repellant. In respect to wettability, the compositions containing sodium carboxymethyl-cellulose are outstanding and hence preferred. The application to artificial yarns and cords, such as regenerated cellulose rayon tire cord is accompanied by improved oven dry tensile strength in the cords as compared to such cords treated by the conventional compositions.

It is to be understood that changes and variations may be made without departing from the spirit and scope of the invention as defined in the appended claims.

We claim:

1. An emulsion comprising water in sufficient quantities to provide the external phase of the emulsion and, as its internal phase, 2 to parts by weight of a water-dispersible polymeric colloid, 1 to parts by weight of a polyethylene glycol ether of a, compound selected from the group consisting of castor oil and hydrogenated castor oil, the ether containing from about 80 to 200 ethoxy groups per molecule, 1 to 5 parts by weight of an alkaline buffer, and about 0.5 to 15 parts by weight of a lubricant comprising at least 0.5 part by weight of a waxy partial ester of an anhydro-hexahydric alcohol and a. fatty acid of at least 16 carbon atoms.

2. The emulsion of claim 1 in which the lubricant comprises an oil in addition to the aforesaid waxy partial ester.

3. The emulsion of claim 1 in which the colloid is polyvinyl alcohol- 4. The emulsion of claim 1 in which the colloid is sodium carboxymethyl cellulose.

5. The emulsion of claim 1 in which the colloid ishydroxyethyl cellulose.

6. The emulsion of claim 1 in. which the buffer is a sodium salt of a fatty acid having at least 12 carbon atoms.

7. The emulsion of claim 1 in which the buffer is sodium oleate.

8. The emulsion of claim 1 in which the bui'-' fer is sodium sorbitol borate.

9. The emulsion of claim 1 in which the colloid is polyvinyl alcohol and the buffer is soloid is polyvinyl alcohol and the buffer is sodium sorbitol borate.

12. As an article of manufacture a flexible base material carrying ,4; to 25% by weight of a coating composition thereon comprising 2 to 10 parts by weight of a water-dispersible polymeric colloid, 1 to 15parts by weight of a polyethylene glycol ether of a compound selected from the'group consisting of castor oil and hydrogenated castor oil, the ether containing from about to 200 ethoxy groups per molecule, 1 to 5 parts by weight of an alkaline buffer, and about 0.5 to 15 parts by weight of a lubricant comprising at least 0.5 part by weight of -a waxy partial ester or an anhydro-hexahydric alcohol and a fatty acid of at least 16 carbon atoms.

13. The article of claim 12 in which the base is a textile strand.

14. The article of claim 12 in which the base is a tire cord of regenerated cellulose of at least 500 denier.

15. The article of claim 12 in which the base is a yarn having its otherwise lively twist reduced or set by the composition.

16. The article of claim 12 in which the base is a yarn of untwisted filaments.

17. The article of claim 12 in which the base is a textile fabric.

18. As an article of manufacture a sheet of cellophane carrying A; to 25% by weight of a coating composition thereon comprising 2 to 10 parts by weight of a water-dispersible polymeric colloid, 1 to 15 parts by weight of a polyethylene glycol ether of a compound selected from the group consisting of castor oil and hydrogenated castor oil, the ether containing from about 80 to 200 ethoxy groups per molecule, 1 to 5 parts by weight of an alkaline buffer, and about 0.5 to 15 parts by weight of a lubricant comprising at least 0.5 part by weight of a waxy partial ester of an anhydro-h-exahydric alcohol and a fatty acid of at least 16 carbon atoms.

CARL SCHLATTER. JOHN B. EISEN. GEORGE D. JEFFERSON.

References Cited in the file of this patent UNITED STATES PA'I'ENTS Number Name Date 1,970,578 "Schoeller et al Aug. 21, 1934 2,003,409 Whitehead June 4, 1935 2,067,888 Chamberlin Jan. 19, 1937 2,201,992 Dreyfus et al. May 28, 1940 2,277,788 Shipp et al. Mar. 31, 1942 2,297,135 Davis et a1 Sept. 29, 1942 2,324,601 Spanagel July 20, 1943 2,348,552 Little May 9, 1944 2,404,240 MacLaurin July 16, 1946 2,436,219 MacLaurin Feb. 17, 1948 2,436,979 Standley Mar. 2, 1948 2,448,571 Balch et a1. Sept. 7, 1948 2,449,215 Goldthwait et a1. Sept. 14, 1948 2,461,043 Eisen Feb. 8, 1949 2,496,776 Caldwell Feb. 7, 1950 2,497,536 Chandler Feb. 14, 1950 

12. AN ARTICLE OF MANUFACTURE A FLEXIBLE BASE MATERIAL CARRYING 1/4 TO 25% BE WEIGHT OF A COATING COMPOSITION THEREON COMPRISING 2 TO 10 PARTS BY WEIGHT OF A WATER-DISPERISBLE POLYMERIC COLLOID, 1 TO 15 PARTS BY WEIGHT OF A POLYETHYLENE GLYCOL ETHER OF A COMPOUND SELECTED FROM THE GROUP CONSISTING OF CASTOR OIL AND HYDROGENATED CASTOR OIL, THE ETHER CONTAINING FROM ABOUT 80 TO 200 THOXY GROUPS PER MOLECULE, 1 TO 5 PARTS BY WEIGHT OF AN ALKALINE BUFFER, AND ABOUT 0.5 TO 15 PARTS BY WEIGHT OF A LUBRICANT COMPRISING AT LEAST 0.5 PART BY WEIGHT OF A WAXY PARTIAL ESTER OF AN ANHYDRO-HEXAHYDRIC ALCOHOL AND A FATTY ACID OF AT LEAST 16 CARBON ATOMS.
 15. THE ARTICLE OF CLAIM 12 IN WHICH THE BASE IS A YARN HAVING ITS OTHERWISE LIVELY TWIST REDUCED OR SET BY THE COMPOSTION. 